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United States Patent |
6,258,963
|
Koch
,   et al.
|
July 10, 2001
|
Benzylidene-.gamma.-butyrolactones, process for their preparation and their
use as UV absorber
Abstract
The invention relates to modified benzylidene-.gamma.-butyrolactones, to a
process for their preparation and to the use as UV absorber, for example
in pharmaceutical and cosmetic compositions, sunscreens, daycare and
haircare products, for improving industrial products, such as paints,
surface coatings, plastics, textiles, packaging materials and rubbers.
Inventors:
|
Koch; Oskar (Gottingen, DE);
Johncock; William (Hoxter, DE);
Langner; Roland (Bevern, DE)
|
Assignee:
|
Haarmann & Reimer GmbH (Holzminden, DE)
|
Appl. No.:
|
458135 |
Filed:
|
December 9, 1999 |
Foreign Application Priority Data
| Dec 11, 1998[DE] | 198 57 252 |
Current U.S. Class: |
549/295; 424/59; 424/60; 549/323 |
Intern'l Class: |
C07D 307/33 |
Field of Search: |
549/295,323
424/59,60
|
References Cited
U.S. Patent Documents
5217709 | Jun., 1993 | Lagrange et al. | 424/47.
|
5961960 | Oct., 1999 | Dilk et al. | 424/59.
|
5965066 | Oct., 1999 | Koch et al. | 252/589.
|
Foreign Patent Documents |
0 044 970 | Jun., 1983 | EP.
| |
2222829 | Mar., 1990 | GB.
| |
Other References
P. Rioult, J. Vialle: "Composes Organiques Sulfures XIV. Condensation Des
Lactones, Thiolactones et Thiolannethiones-2 Avec Les Aldehydes
Aromatiques et le Sulfure de Carbone", Bull. Soc. Chim. FR., Nr. 11, 1968,
Seiten 4477-4483, XP000882402.
H. Zimmer et al: "Substituted Gama-Lactones, IV, Some Aldehyde
Condensations with Delta (Beta, Gamma)-Angelica- and Gamma-Valerolactone",
J. Org. Chem, Bd 25, 1960, Seiten 838-839, XP000882308.
H. Zimmer et al, "Substituted Gamma-Lactones, XIII, Nitration of
Substituted Alpha-Benzylidene-Gamma-Butyrolactones", J. Org. Chem., Bd 29,
1964, Seiten 952-929, XP000882311.
Datta et al, Tetrahedron 43(22), pp. 5367-5374, 1987.*
Torabi et al, J. Org. Chem., 34(12), pp. 3792-3796, 1969.*
Zimmer et al, J. Org. Chem., 25, pp. 838-389, 1960.*
Matsuo et al, Chem. Pharm. Bull, 37(10), pp. 2803-2806, 1989.
|
Primary Examiner: Trinh; Ba K.
Attorney, Agent or Firm: Gil; Joseph C., Cheung; Noland J.
Claims
What is claimed is:
1. A benzylidene-.gamma.-butyrolactone comprising the general formula
##STR3##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms, wherein R.sup.1 to R.sup.5 includes at
least one C.sub.2 chain.
2. A benzylidene-.gamma.-butyrolactone according to claim 1, wherein the
lactone ring is trisubstituted (R.sup.1, R.sup.3 and R.sup.4 =alkyl),
wherein an alkyl group includes at least one C.sub.2 chain.
3. A benzylidene-.gamma.-butyrolactone according to either of claim 1,
wherein the benzylidene ring is substituted in the para-position by a
methoxy radical, and R.sup.1 is ethyl, R.sup.2 is hydrogen and R.sup.3
/R.sup.4 is methyl.
4. A composition comprising at least one benzylidene-.gamma.-butyrolactone
having the general formula
##STR4##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms, wherein R.sup.1 to R.sup.5 includes at
least one C.sub.2 chain.
5. A composition according to claim 4, wherein said composition comprises
from 0.1 to 15% by weight of benzylidene-.gamma.-butyrolactone, based on
the total weight of the preparation.
6. A composition according to claim 5, wherein said composition comprises
from 1 to 10% by weight of benzylidene-.gamma.-butyrolactone, based on the
total weight of the preparation.
7. A composition according to claim 6, wherein said composition comprises
from 2 to 7% by weight of benzylidene-.gamma.-butyrolactone, based on the
total weight of the preparation.
8. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone is a UV absorber and also a solvent.
9. A composition according to claim 4, wherein said composition comprises
additives and optionally, UV absorbers and optionally, pigments.
10. A composition according to claim 4, wherein said composition is an
emulsion, milk, lotion, cream, gel, aerosol, shampoo, conditioner,
intensive conditioner, spray or any other customary cosmetic or
pharmaceutical preparation.
11. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone has high UV protection even at low use
concentrations.
12. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone has excellent photostability and thermal
stability.
13. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone has good solubility in cosmetic
solvents.
14. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone are crystalline, oil-soluble UV
absorbers and have excellent solubility.
15. A composition according to claim 4, wherein said
benzylidene-.gamma.-butyrolactone shows good pH stability.
16. A composition according to claim 4, wherein
benzylidene-.gamma.-butyrolactone is colorless, neutral in odor and
water-resistant.
17. A process for the preparation of compositions comprising the mixing of
at least one benzylidene-.gamma.-butyrolactone having the general formula
##STR5##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms, wherein R.sup.1 to R.sup.5 includes at
least one C.sub.2 chain;
with additives and optionally, UV absorbers and optionally, pigments.
18. A sunscreen or daycare product for protecting human skin and hair
against harmful UV radiation comprising at least one
benzylidene-.gamma.-butyrolactone having the general formula
##STR6##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms, wherein R.sup.1 to R.sup.5 includes at
least one C.sub.2 chain.
19. An industrial product comprising at least one
benzylidene-.gamma.-butyrolactone having the general formula
##STR7##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms,
wherein R.sup.1 to R.sup.5 includes at least one C.sub.2 chain.
20. A solvent for solid UV absorbers which have poor solubility within a
cosmetic preparation comprising at least one
benzylidene-.gamma.-butyrolactone having the general formula
##STR8##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most 4
are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or cycloalkyl,
and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 form a carbocyclic ring
having from 5 to 7 ring atoms, wherein R.sup.1 to R.sup.5 includes at
least one C.sub.2 chain.
21. A benzylidene-.gamma.-butyrolactone according to claim 1, wherein said
benzylidene-.gamma.-butyrolactone is selected from the group consisting of
p-methoxy-benzylidene-3-ethyl-4,4-dimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3,4-dimethyl-4-butyl-.gamma.-butyrolactone, or
p-methoxybenzylidene-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone.
Description
FIELD OF THE INVENTION
The invention relates to modified benzylidene-.gamma.-butyrolactones, to a
process for their preparation and to the use as UV absorber, for example
in pharmaceutical and cosmetic compositions, sunscreens, daycare and
haircare products, for improving industrial products, such as paints,
surface coatings, plastics, textiles, packaging materials and rubbers.
BACKGROUND OF THE INVENTION
Depending on their wavelength, UV rays are divided in UV-A rays (320-400
nm) and UV-B rays (280-320 nm). The harmful effect, in particular the
occurrence of sunburn (erythema), increases not only with the duration of
exposure but also with decreasing wavelength and is thus significantly
more strongly marked in the case of UV-B radiation than in the case of
UV-A radiation. Since erythemas can occur even after short exposure to the
sun, in some cases after 20-30 minutes, efficient protection against this
radiation is of particular importance.
For this area of UV protection, a number of UV-B absorbers are already
known from the prior art. Examples mentioned are camphor derivatives,
salicylic acid derivatives, benzophenones, cinnamates, benzimidazoles and
triazines. One example of benzylidene-.gamma.-butyrolactones is described
in European Patent Application EP-A 44970. These are compounds of the
formula
##STR1##
in which
R is a C.sub.1 -C.sub.15 -alkyl radical, branched or unbranched, phenyl or
benzyl.
However, all of these compounds have the disadvantages that they are either
in the form of a solid and thus have only limited solubility in the
cosmetic preparations, exhibit only low absorption or have photostability
which does not meet the necessary criteria and are thus unsatisfactory.
SUMMARY OF THE INVENTION
Accordingly, the object of the present invention is to provide improved
UV-B absorbers. This object is achieved by
benzylidene-.gamma.-butyrolactones of the general formula
##STR2##
wherein
R is hydrogen or C.sub.1 -C.sub.6 -alkyl or cycloalkyl, and
R.sup.1 to R.sup.5 independently of one another are hydrogen, but at most
4, are hydrogen at the same time, or C.sub.1 -C.sub.8 -alkyl or
cycloalkyl, and also R.sup.1 /R.sup.2 and/or R.sup.3 /R.sup.4 can form a
carbocyclic ring having from 5 to 7 ring atoms.
According to the present invention, particular preference is given to
benzylidene-.gamma.-butyrolactones in which the lactone ring is
trisubstituted at R.sup.1, R.sup.3 and R.sup.4 by an alkyl, where an alkyl
group includes at least one C.sub.2 chain. Likewise preferred are
benzylidene-.gamma.-butyrolactones whose benzylidene ring is substituted
in the para-position by a methoxy radical, and R.sup.1 is an ethyl
radical, R.sup.2 is hydrogen, and R.sup.3 /R.sup.4 is a methyl radical.
Specific benzylidene-.gamma.-butyrolactones compounds of the present
invention include: p-Methoxybenzylidene-4-methyl-.gamma.-butyrolactone,
p-methoxybenzylidene-4-butyl-.gamma.-butyrolactone,
p-methoxybenzylidene-4,4-dimethyl-.gamma.-butyrolactone,
p-methoxy-benzylidene-3,4-dimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3,4,4-trimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3-methyl-4-pentyl-.gamma.-butyrolactone,
p-methoxybenzyl-idene-3-methyl-4-hexyl-.gamma.-butyrolactone,
o,p-dimethoxybenzylidene-4-butyl-.gamma.-butyrolactone,
o,p-dimethoxybenzylidene-4,4-dimethyl-.gamma.-butyrolactone,
o,p-dimethoxybenzylidene-3,4-dimethyl-.gamma.-butyrolactone,
m,p-dimethoxybenzylidene-4-butyl-.gamma.-butyrolactone,
m,p-dimethoxybenzyl-idene-4,4-dimethyl-.gamma.-butyrolactone,
m,p-dimethoxybenzylidene-3,4-dimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3-ethyl-4,4-dimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3,4-dimethyl-4-butyl-.gamma.-butyro-lactone,
p-methoxybenzylidene-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone.
Particularly preferred benzylidene-.gamma.-butyrolactones include
p-methoxy-benzylidene-3-ethyl-4,4-dimethyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3,4-dimethyl-4-butyl-.gamma.-butyrolactone,
p-methoxybenzylidene-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone.
The benzylidene-.gamma.-butyrolactones according to the present invention
can be prepared in accordance with the prior art by aldol condensation of
substituted benzaldehydes, for example anisaldehyde, with correspondingly
substituted .gamma.-butyrolactones, for example
.beta.-ethyl-.gamma.,.gamma.-dimethyl-.gamma.-butyrolactone.
Additionally, the benzylidene-.gamma.-butyrolactones according to the
present invention are particularly suitable as UV absorbers and solvents
for solid UV absorbers, which have relatively poor solubility within a
pharmaceutical or cosmetic preparation. Accordingly, the present invention
also provides compositions which comprise the above-mentioned
benzylidene-.gamma.-butyrolactones and are suitable for protecting against
harmful UV radiation. In this connection, the compositions according to
the present invention can comprise one or more of the
benzylidene-.gamma.-butyrolactones according to the invention.
Preference is given to compositions which comprise from 0.1 to 15% by
weight of benzylidene-.gamma.-butyrolactones according to the present
invention, based on the total weight of the preparation. Particular
preference is given to compositions comprising from 1 to 10% by weight,
and most preferably comprising from 2 to 7% by weight, of
benzylidene-.gamma.butyrolactone according to the present invention.
According to the present invention, the above-mentioned compositions are
preferably suitable as sunscreens or daycare products for protecting human
skin and hair, in particular hair already predamaged by permanent waving,
coloring and bleaching, against harmful UV radiation.
According to the present invention, the compositions can also be mixed with
additives known per se and/or known UV absorbers of other classes of
substance and/or known pigments.
Examples of common additives are emulsifiers, surface-active compounds,
lanolin, petroleum jelly, water, triglycerides of fatty acids,
polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty
acid ester such as, for example, isopropyl palmitate, isooctyl sterate,
diisopropyl adipate etc., natural or synthetic oils or waxes, thickeners,
such as, for example, hydroxyethylcellulose, bentonite, etc.,
preservatives, moisturizers, vitamins, skin-lightening active ingredients
such as, for example, hydroquinones, arbutin, kojic acid and derivatives,
ascorbic acid and derivatives, glutathione, hydroxybenzaldoximes, e.g.,
4-hydroxy-3-methoxybenzaldehyde oxime, antioxidants such as, for example,
BHT, vitamin derivatives, catechol derivatives, e.g., epigallocatechol
gallate or 3,4-dihydroxybenzaldehyde oxime, complexing agents such as, for
example, EDTA and derivatives, insect repellents such as, for example,
DEET or IR 3535, silicone oils, glycerol, ethyl alcohol and perfume oils.
The list of additives is not limited to the examples given. Pigments which
can be added are, for example, titanium dioxide, zinc oxide, pearlizing
pigments or color pigments.
Examples of traditional UV absorbers include p-aminobenzoic acid, ethyl
p-amino-benzoate (25 mol) ethoxylated, 2-ethylhexyl
p-dimethyl-aminobenzoate, ethyl p-aminobenzoate (2 mol) N-propoxylated,
glycerol p-aminobenzoate, homomenthyl salicylate, 2-ethylhexyl salicylate,
triethanolamine salicylate, 4-isopropylbenzyl salicylate, methyl
anthranilate, ethyl diisopropylcinnamate, 2-ethylhexyl
p-methoxy-cinnamate, methyl diisopropylcinnamate, isoamyl
p-methoxycinnamate, p-methoxy-cinnamic acid diethanolamine salt, isopropyl
p-methoxycin-namate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl
2-cyano-3,3'-diphenyl acrylate, 2-phenyl-benzimidazolesulphonic acid and
salts, 3-(4'-trimethylammonium)-benzylidene-bornan-2-one methylsulphate,
terephthalylidene-dibornanesulphonic acid and salts,
4-t-butyl-4'-methoxydibenzoylmethane, .beta.-imidazole-4(5)-acrylic acid
(urocanic acid). 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulphonic acid,
dihydroxy-4-methoxybenzophenone, 2,4-dihydroxy-benzophenone,
tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2-hydroxy-4-n-octoxybenzophenone,
2-hydroxy-4-methoxy-4'-methylbenzophenone,
3-(4'sulpho)benzylidene-bornan-2-one and salts,
3-(4'-methylbenzylidene)-d,1camphor, 3-benzylidene-d,1-camphor,
4-isopropyldibenzoylmethane,
2,4,6trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine,
phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt and N-[(2 and
4)-[2-(oxoborn-3ylidene)methyl]benzyl]-acrylamide polymer, benzylidene
malonate polymer,
2,2'-methylene-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-
phenol), 2,2'-(1,4-phenylene)bis-1H-benzimidazol-4,6-disulphonic acid,
monosodium salt,
2,4-bis-((4-(2-ethyl-hexyloxy)-2-hydroxy)-phenyl)-6-(4-methoxyphenyl)-(1,3
,5)-triazine.
UV absorbers which have proven to be particularly suitable for combination
with the agents according to the present invention are 2-ethylhexyl
p-methoxycinnamate, isoamyl p-methoxycinnamate,
2-phenylbenzimidazolesulphonic acid, 3-(4'-methylbenzylidene)-d,1-camphor,
2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl salicylate,
4-tert-butyl-4'-methoxydibenzoylmethane and
phenylene-bis-benzimidazyl-tetrasulphonic acid disodium salt, indanylidene
derivatives according to DE 19 631 863 and benzazol derivatives according
to DE 19 648 010.
The present invention further provides for the use of the agents according
to the present invention in combination with conventional UV absorbers for
enhancing the protection against harmful UV radiation above the degree of
protection which is achieved using equal amounts of conventional UV
absorbers alone or the agents alone (synergistic effect).
Furthermore, the agents according to the present invention can also be
combined with conventional UV absorbers which are used for the protection
of industrial products, such as paints, surface coatings, plastics,
textiles, packaging materials or rubber.
Examples of such UV absorbers are compounds from the group consisting of
benzotriazoles, benzophenones, triazines, cinnamic esters and
oxalanilides.
The compositions according to the present invention can be in the form of
any currently customary cosmetic or pharmaceutical preparations. For
example, they can be supplied as emulsion, milk, lotion, cream, gel,
aerosol, shampoo, conditioner, intensive conditioner or spray.
Surprisingly, the compositions which comprise
benzylidene-.gamma.-butyrolactone in accordance with the present invention
are characterized by a combination of desirable properties.
The agents have the advantageous properties according to the present
invention in that they have high UV protection even at low use
concentrations, excellent photo-stability and thermal stability and good
solubility in cosmetic solvents. In addition, the crystalline, oil-soluble
UV absorbers have, in accordance with the present invention, excellent
solubility in cosmetic solvents. The agents have, in accordance with the
invention, good compatibility with cosmetic bass and good pH stability,
are colorless, neutral in odor and water-resistant. In addition, the
agents according to the present invention can be incorporated without
problems into cosmetic preparations and exhibit good stability under use
conditions and good compatibility with packaging materials. Moreover, the
compositions according to the present invention do not cause any
discoloration of textiles and can be washed out easily.
The application is illustrated in more detail below by reference to the
examples:
EXAMPLES
1. Benzylidene-.gamma.-butyrolactones according to the present invention
and their preparation
By way of example for the preparation of the
benzylidene-.gamma.-butyrolactones according to the invention, the
preparation of p-methoxybenzylidene-4-methyl-.gamma.-butyrolactone as
Example 1 may be illustrated in more detail.
Example 1
p-Methoxybenzylidene-4-methyl-.gamma.-butyrolactone
74 g (0.5 mol) of 4-methyl-.gamma.-butyrolactone are added to a suspension
of 27 g (0.50 mol) of sodium methoxide in 400 g of methyl tert-butyl ether
and, over the course of 1 h, 68 g (0.5 mol) of anisaldehyde are added
thereto with stirring at room temperature. The mixture is maintained under
reflux for a further 1 h and then cooled, and 200 g of iced water are
added to the mixture and the pH is adjusted to 5 using 10% sulphuric acid.
After the phases have separated, the product is distilled. This gives 65 g
of the desired compound in a yield of 48% of theory. The specific
absorbance E1/1 of the novel compound according to the present invention
is 1.250, measured at a wavelength of .lambda..sub.max 310 nm.
Example 2
p-Methoxybenzylidene-4,4-dimethyl-.gamma.-butyrolactone
Analogous process using 4,4-dimethyl-.gamma.-butyrolactone. E1/1 1.200
(.lambda..sub.max 310 nm).
Example 3
p-Methoxybenzylidene-3,4-dimethyl-.gamma.-butyrolactone
Analogous process using 3,4-dimethyl-.gamma.-butyrolactone. E1/1 1.050
(.lambda..sub.max 314 nm).
Example 4
p-Methoxybenzylidene-3,4,4-trimethyl-.gamma.-butyrolactone
Analogous process using 3,4,4-trimethyl-.gamma.-butyrolactone. E1/1 1.060
(.lambda..sub.max 312 nm).
Example 5
p-Methoxybenzylidene-3-ethyl-4,4-dimethyl-.gamma.-butyrolactone
Analogous process using 3-ethyl-4,4-dimethyl-.gamma.-butyrolactone. E1/1
940 (.lambda..sub.max 312 nm).
Example 6
p-Methoxybenzylidene-3-methyl-4-pentyl-.gamma.-butyrolactone
Analogous process using 3-methyl-4-pentyl-.gamma.-butyrolactone. E1/1 830
(.lambda..sub.max 313 nm).
Example 7
p-Methoxybenzylidene-3,4-dimethyl-4-butyl-.gamma.-butyrolactone
Analogous process using 3,4-dimethyl-4-butyl-.gamma.-butyrolactone. E1/1
810 (.lambda..sub.max 312 nm).
Example 8
p-Methoxybenzylidene-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
Analogous process using 3,4-dimethyl-4-ethyl-.gamma.-butyrolactone. E1/1
960 (.lambda..sub.max 311 nm).
2. Compositions according to the present invention, their preparation and
determination of the sun protection factor:
The composition and the preparation procedure for various sunscreens
according to the present invention are listed in Examples 9 to 14. In this
connection, (O/W) indicates that it is an oil-in-water emulsion. The
abbreviation (W/O) indicates a water-in-oil emulsion. Example 15 describes
the composition and preparation of a sunscreen oil, Example 16 a sunscreen
cream or a sunscreen gel, and Example 17 discloses the constituents and
preparations of a hair shampoo according to the present invention.
Example 9
Sunscreen lotion (O/W)
PREPARATION PROCEDURE:
Part A: Melt at about 80.degree. C.
Part B: Heat to about 90.degree. C., add Part B to Part A with stirring.
Part C: Disperse Carbopol in water until lump-free, neutralize the sodium
hydroxide solution to give a gel, add to Part A/B at about 60.degree. C.
Stir until the temperature drops to room temperature.
Part D: Perfume the emulsion at about 30.degree. C., check the pH (6.5 to
7.0).
TABLE 1
CONSTITUENTS %
A) Arlatone 983 S 1.75
Brij 76 1.25
Lanette O 1.15
Myritol 318 15.00
Cetiol SN 15.00
Phenonip 0.20
UV absorber 5.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
1-10%
B) Water, dist. 31.65
1,2-Propylene glycol 2.00
Phenonip 0.30
C) Water, dist. 25.00
Carbopol 2984 0.30
Sodium hydroxide, 10% in water 1.00
D) Perfume oil 0.40
Example 10
Sunscreen milk (W/O)
PREPARATION PROCEDURE:
Part A: Thorough melt at about 90.degree. C.
Part B: Heat to bout 95.degree. C., then add Part B to Part A with
stirring. Stir until the temperature drops to room temperature.
Part C: Ad Part C at 30.degree. C. and then homogenize.
TABLE 2
CONSTITUENTS %
A) Dehymuls PG PH 5.00
Permulgin 3220 0.50
Zinc stearate 0.50
Myritol 318 15.00
Cetiol SN 15.00
UV absorber 5.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
B) Water, dist. 52.50
Glycerol 86% 5.00
Magnesium sulphate 7 H.sub.2 O 0.50
Phenonip 0.50
C) Perfume oil 0.50
Example 11
Sunscreen lotion (O/W)
PREPARATION PROCEDURE:
Part A: Melt at about 80.degree. C.
Part B: Heat at about 90.degree. C. Add Part B to Part A with stirring.
Part C: Disperse Carbopol in water until lump-free, neutralize with sodium
hydroxide solution to give a gel, add to Part A/B at about 60.degree. C.
Stir until the temperature drops to room temperature.
Part D: Perfume the emulsion at about 30.degree. C., check the pH (6.5 to
7.0).
TABLE 3
CONSTITUENTS %
A) Arlatone 983 S 1.75
Brij 76 1.25
Lanette O 1.15
Myritol 318 15.00
Cetiol SN 15.00
Finsolv TN 5.00
Phenonip 0.20
UV absorber 4.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
Parsol 1789 1.50
B) Water, dist. 26.15
1,2-Propylene glycol 2.00
Phenonip 0.30
C) Water, dist. 25.00
Carbopol 2984 0.30
Sodium hydroxide, 10% strength in water 1.00
D) Perfume oil 0.40
Example 12
Sunscreen lotion (O/W)
PREPARATION PROCEDURE:
Part A: Melt at about 80.degree. C.
Part B: Heat at about 90.degree. C. Add Part B to Part A with stirring.
Part C: Disperse Carbopol in water until lump-free, neutralize with sodium
hydroxide solution to give a gel, add to Part A/B at about 60.degree. C.
Stir until the temperature drops to room temperature.
Part D: Perfume the emulsion at about 30.degree. C., check the pH (6.5 to
7.0).
TABLE 4
CONSTITUENTS %
A) Arlatone 983 S 1.75
Brij 76 1.25
Lanette O 1.15
Myritol 318 12.00
Cetiol SN 12.00
UV absorber 7.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
NEO HELIOPAN .RTM. E 1000 7.00
Phenonip 0.20
B) Water, dist. 28.65
1,2-Propylene glycol 2.00
Phenonip 0.30
C) Water, dist. 25.00
Carbopol 2984 0.30
Sodium hydroxide, 10% strength in water 1.00
D) Perfume oil 0.40
Example 13
Sunscreen lotion (O/W)
PREPARATION PROCEDURE:
Part A: Melt at about 80.degree. C., then thoroughly disperse Eusolex TA.
Part B: Heat at about 90.degree. C. without Veegum and Natrosol, then
disperse Veegum and Natrosol, add Part B to Part A with stirring. Stir
until the temperature drops to room temperature.
Part C: Ad Part C at 30.degree. C. and then homogenize.
Check the pH (7.0-7.5).
TABLE 5
CONSTITUENTS %
A) Arlacel 165 3.00
Eumulgin B 2 1.00
Lanette 1.00
Myritol 318 4.00
Cetiol OE 2.00
Abil 100 1.00
Bentone Gel MIO 3.00
Cutina CBS 1.00
Phenonip 0.20
NEO HELIOPAN .RTM. OS (octyl salicylate) 3.00
NEO HELIOPAN .RTM. AV (octyl methoxycinnamate) 5.00
NEO HELIOPAN .RTM. E 1000 (isoamyl p-methoxycinnamate) 5.00
NEO HELIOPAN .RTM. MBC (4-methylbenzylidene camphor) 1.00
Eusolex TA 3.00
UV absorber p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-
3.00
butyrolactone
B) Water, dist. 45.60
Glycerol, 86% strength 3.00
Phenonip 0.30
Veegum Ultra 1.00
Natrosol 250 HHR 0.30
NEO HELIOPAN .RTM. HYDRO, used as a 15% strength 13.30
solution after neutralization with sodium hydroxide (phenyl
benzimidazole sulphonic acid) corresponds to active
substance: 2.0%
C) Perfume oil 0.30
Example 14
Sunscreen lotion (O/W)
PREPARATION PROCEDURE:
Part A: Thoroughly melt at about 90.degree. C. (without ZINKOXID NEUTRAL
H&R). Then thoroughly disperse ZINKOXID NEUTRAL H&R.
Part B: Heat at about 95.degree. C., then add Part B to Part A with
stirring. Stir until the temperature drops to room temperature.
Part C: Add Part C at 30.degree. C. and then homogenize.
TABLE 6
CONSTITUENTS %
A) Arlacel 1689 3.50
Finsolv TN 6.00
NEO HELIOPAN .RTM. E 1000 7.00
(isoamyl p-methoxycinnamate)
Uvinul T 150 (octyl triazone) 1.00
UV absorber p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.- 3.00
butyrolactone
Copherol F 1250 2.00
Permulgin 2550 1.00
Myritol 318 6.00
Cetiol SN 6.00
ZINKOXID NEUTRAL H&R (zinc oxide) 7.00
B) Water, dist. 51.70
Glycerol 86% strength 5.00
Phenonip 0.50
C) Perfume oil 0.30
Example 15
Sunscreen oil
PREPARATION PROCEDURE:
Thoroughly mix and constituents.
TABLE 7
CONSTITUENTS %
A) NEO HELIOPAN .RTM. E 1000 7.50
(isoamyl p-methoxycinnamate)
NEO HELIOPAN .RTM. OS (octyl salicylate) 5.00
UV absorber 3.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
Myritol 318 34.70
Diisopropyl adipate 5.00
Olive oil 1.00
Jojoba oil 1.00
Macadamia nut oil 1.00
Tocopherol oil 1.00
Isopropyl myristate 35.00
Antaron V-216 5.00
Phenonip 0.50
Perfume oil 0.30
Example 16
Sunscreen cream gel
PREPARATION PROCEDURE:
Part A: dissolve ingredients in the water.
Part B: Mix all constituents (without Permulen and Carbopol). Dissolve NEO
HELIOPAN.RTM. MBC and UV absorber according to formula (I) with gentle
warming. Disperse Carbopol and Permulen. Then add Part B to Part A and mix
vigorously for 45 minutes.
Part C: Add triethanolamine to Part A/B with stirring. Continue stirring
until the product is homogeneous. Check the pH (about 7.0).
TABLE 8
CONSTITUENTS %
A) Water, dist. 75.35
Phenonip 0.50
EDTA B liquid 0.10
B) NEO HELIOPAN .RTM. AV (octyl methoxycinnamate) 7.00
NEO HELIOPAN .RTM. 303 (octocrylene) 3.00
NEO HELIOPAN .RTM. MBC (4-methylbenzylidene camphor) 1.00
UV absorber 3.00
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
Cetiol SN 5.00
Eutanol G 3.00
Lameform TG 1 1.00
Perfume oil 0.30
Permulen TR-1 0.25
Carbopol 954 0.05
C) Triethanolamine 0.45
Example 17
Hair shampoo
Part A: Dissolve UV absorber in NEO HELIOPAN.RTM. E 1000 and Phenonip and
with gentle warming, then add Arlatone G and perfume oil and mix well.
Weigh in the remaining constituents.
Part B: Dissolve polymer in the water with stirring, and add and dissolve
the remaining constituents. Add Part B to Part A and stir (check the pH,
about 5.5).
TABLE 9
CONSTITUENTS %
A) Genapol LRO liquid 18.00
Texapon MG3 36.00
Lamepon S 6.00
Perfume oil 0.60
Phenonip 0.50
Arlatone G 2.00
UV absorber 0.50
p-Methoxybenzyliden-3,4-dimethyl-4-ethyl-.gamma.-butyrolactone
B) Water, dist. 34.00
Polymer JR 400 0.20
D-Panthenol 1.00
Sodium chloride 1.00
Sodium hydroxide, 10% strength in water 0.20
PREPARATION PROCEDURE:
3. Commercially available substances used to prepare the compositions
according to the invention:
The commercially available substances used in Point 2 to prepare the
compositions according to the invention, and their suppliers are
summarized below:
TABLE 10
Trade name Chemical name Supplier
Abil 100 Polydimethylsiloxane 7
Antaron V-216 Vinylpyrrolidone/hexadecene copolymer 18
Arlacel 1689 Sorbitan monooleate/propylglyceryl-3- 4
ricinoleate
Arlacel 165 Glycerol stearate/polyethylene glycol 4
(MW 100) stearate mixture
Arlatone G hydrogenated with 25 mol of ethylene oxide 4
Arlatone 983 S Polyethylene glycol (MW 5) glyceryl stearate 4
Baysilone Fluid PK 20 Silicone oil 5
Betone Gel MIO Mineral oil, quaternium-18 hectorite, 17
propylene carbonate
Brij 76 Polyethylene glycol (MW 10) stearyl ether 4
Carbopol 2984 Polyacrylic acid 2
Carbopol 954 Polyacrylic acid 2
Cetiol HE Polyol fatty acid ester 3
Cetiol OE Dicaprylyl ether 3
Cetiol SN Cetyl/stearyl isononanoate 3
Copherol F 1250 D-.alpha.-Tocopheryl acetate 3
Cutina CBS Glycerol stearate, cetyl/stearyl alcohol cetyl
3
palmitate, coconut glycerides
Dehymuls PG PH Polyglycerol poly-12-hydroxystearate 3
Diisopropyl adipate Diisopropyl adipate 3
D-Panthenol Panthothenyl alcohol 15
EDTA B liq. Tetrasodium ethylenediaminetetraacetic acid 6
Eusolex TA Titanium dioxide 13
Eutanol G 2-Octyldodecanol 3
Eumulgin B2 Cetyl/stearyl alcohol, etherified with 20 mol of
3
ethylene oxide
Finsolv TN Alkyl benzoate 23
Genapol LRO liq. Sodium lauryl sulphate 9
Glycerol 1,2,3-Propanetriol 3
Isopropyl myristate Isopropyl myristate 3
Jojoba oil Jojoba oil 19
Lameform TGI Triglycerol diisostearate 3
Lameform S Protein/coconut fatty acid condensate. 3
potassium salt
Lanette 0 Cetyl/stearyl alcohol mixture 3
Macadamia nut oil Macadamia nut oil 20
Myritol 318 Capryl/capric triglyceride 3
Natrosol 250 HHR Hydroxyethylcellulose 11
NEO HELTOPAN .RTM.AV Isooctyl p-methoxycinnamate 1
NEO HELIOPAN .RTM.BB 2-Hydroxy-4-methoxybenzophenone 1
NEO HELIOPAN .RTM.E 1000 Isoamyl p-methoxycinnamate 1
NEO HELIOPAN .RTM.HYDRO Phenylbenzimidazolesulphonic acid 1
NEO HELIOPAN .RTM.BC 3-(4-Methylbenzylidene)-d, 1-camphor 1
NEO HELIOPAN .RTM.OS 1-Ethylhexyl salicylate 1
NEO HELIOPAN .RTM.303 Isooctyl .alpha.-phenyl-.beta.-cyanocinnamate 1
Olive oil Olive oil 21
Parsol 1789 Butylmethoxydibenzoylmethane 12
Permulgin 2550 Wax 14
Permulgin 3220 Wax 14
Permulen TR 1 Polyacrylate 2
Phenonip Mixture of p-hydroxybenzoic esters and 8
phenoxyethanol
Polymer JR 400 Polyquaternium-10 21
1,2-Propylene glycol 1,2-Propanediol 6
Texapon MG 3 Magnesium lauryl sulphate/disodium lauryl 3
sulphosuccinate
Tocopherol oil Soya oil with D-.alpha.-tocopherol 22
Uvinul T 150 Isooctyl triazinyl-p-aminobenzoate 6
Veegum Ultra Magnesium aluminium silicate 10
ZINC OXIDE NEUTRAL Zinc oxide 1
H&R
Zinc stearate Zinc stearate 16
Suppliers
TABLE 11
1. Haarmann & Reimer GmbH, Holzminden
2. B. F. Goodrich Company, Neuss
3. Henkel KGaA, Dusseldorf
4. ICI Speciality Chemicals, Frankfurt
5. Bayer AG, Leverkusen
6. BASF, Ludwigshafen
7. Goldschmidt AG, Essen
8. Nipa Lab, Ltd., Pontypridd Mid Glam., Wales/GB
9. Hoechst AG, Frankfurt
10. R. T. Vanderbilt Company Inc., Norwalk/USA
11. Hercules Inc., Wilmington, Delaware/USA
12. Hoffmann-LaRoche, Basle/CH
13. E. Merck, Darmstadt
14. Koster Keunen Holland BV, Bladl/NL
15. Akzo Chemie GmbH, Duren
16. Chemische Werke Barlocher, Munich
17. Rheox Inc., Hightstown, New Jersey/USA
18. ISP Global Technologies Deutschland GmbH, Frechen
19. Henry Lamotte, Bremen
20. Erhard Wagner GmbH, Bremen
21. Nordmann & Rassmann GmbH & Co., Hamburg
22. Richter GmbH, Berlin
23. Witco Surfactants GmbH, Steinau a.d. Stra.beta.e
Although the invention has been described in detail in the foregoing for
the purpose of illustration, it is to be understood that such detail is
solely for that purpose and that variations can be made therein by those
skilled in the art without departing from the spirit and scope of the
invention except as it may be limited by the claims.
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